Production process for manufacturing low molecular weight water soluble acrylic polymers as drilling fluid additives

ABSTRACT

Disclosed is a process for preparing relatively low molecular weight, water absorbing, acrylic polymers for use as drilling fluid additives by aqueous polymerization of (A) an acrylic monomer, such as acrylic acid neutralized 0 to 100 mole percent with, for example, ammonia, and/or an alkali such as Na 2  O 3 , and/or an amine; with (B) acrylamide in a mole ratio of 70 to 100 mole percent (A) to 30:0 mole percent (B). The molecular weight is limited to 1,000 to 50,000, such as by adding a chain transfer agent to the polymerization mixture, to achieve excellent results as a drilling fluid additive. The monomer, such as partially neutralized acrylic acid, is polymerized in aqueous solution in the presence of a polymerization initiator without external heating while allowing water to evaporate off. A substantially dry water soluble polymer (less than 15 weight percent water) is achieved when polymerization is completed by utilizing the exothermic heat of polymerization and crosslinking to drive off water without the need for additional heating to obtain a dry solid.

This is a division of application Ser. No. 816,290 filed Jan. 1, 1986,now U.S. Pat. No. 4,709,767.

FIELD OF THE INVENTION

The present invention relates to a method of manufacturingwater-soluble, low molecular weight acrylic resins having new andunexpected capabilities of lowering the viscosity of aqueoussuspensions, such as drilling fluids.

BACKGROUND OF THE INVENTION

Low molecular weight polyacrylate resins have been used as defloculantsor dispersants in waterbased drilling fluids or dispersants as disclosedin U.S. Pat. Nos. 2,552,775 and 4,521,578; and 3,764,530.

One of the processes for polymerizing acrylic acid and acrylates isaqueous solution polymerization. The polymer obtained by this process issoluble in water, is obtained in an aqueous solution and may be dried toa dry product before use in aqueous solution. Thus, the aqueous solutionmust be dehydrated (dried) to obtain a water-soluble resin in thedesired solid or powder form. It is nevertheless difficult to dry thereaction product efficiently by the usual rotary drum roller method orspray drying method because care must be taken to avoid cross-linkingand an insoluble product which results from overheating during drying.

SUMMARY OF THE INVENTION

In brief, the present invention is directed to a process for preparingwater-soluble, acrylate resins by aqueous polymerization of (A) acrylicacid neutralized 0 to 100 mole percent with, for example, ammonia,and/or alkali and/or an amine; with (B) acrylamide in a mole ratio of 70to 100 mole percent (A) to 30:0 mole percent (B) to obtain a lowmolecular weight, water-soluble resin.

In accordance with the present invention, a heated aqueous solutioncomprising (A) an acrylic type monomer, such as acrylic acid neutralized0 to 100 mole percent with, for example, ammonia, and/or alkali and/oran amine is subjected to polymerization in the presence of apolymerization initiator without external heating while allowing waterto evaporate off to from a water-soluble polyacrylate resin for use as aviscosity reducing agent in aqueous suspensions.

Accordingly, an object of the present invention is to provide a processfor preparing a water-soluble polyacrylate resin of low molecular weightfor use as a viscosity reducing agent in a drilling fluid by aqueoussolution polymerization to obtain a dry polymer (15% or less water)without any additional dehydrating or drying step.

Another object of the present invention is to provide a process forpreparing a polyacrylate resin by polymerization of acrylic acidneutralized 0 to 100 mole percent, having a molecular weight of about1,000 to about 50,000 to obtain a dry resin without external heatingduring polymerization.

Another object of the present invention is to provide a process forpreparing a polyacrylate resin by co-polymerization of acrylic acidneutralized 0 to 100 mole percent, with acrylamide in proportions of 0to 30 mole percent acrylamide and 70-100 mole percent acrylic acid oracrylic derived monomer.

The above and other objects and advantages of the present invention willbecome apparent from the following detailed description of the preferredembodiment.

BRIEF DESCRIPTION OF THE DRAWING

The FIG. 1 is a graph showing the reduction in apparent viscosity (AV)in centipoises, plastic viscosity (PV) in centipoises, and yield point(YP) in pounds/100 ft² upon the addition of the low molecular weightpolymer of the present invention to a typical drilling fluid having 92pounds of bentonite per 55 gal. barrel.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

In accordance with the present invention an acrylic-type resin isprepared by aqueous solution polymerization while dehydrating or dryingthe reaction product during polymerization by utilizing the exothermicheat from the polymerization reaction for drying.

The acrylic type monomers capable of polymerization in accordance withthe present invention to provide low molecular weight, water-solubleresins useful for lowing the viscosity of aqueous suspensions includethe linear organic polymers having no, to very little, crosslinkingbetween the individual polymer chains. Preferred monomers includeacrylic acid; acrylamide; acrylic acid salts of alkali metals andammonium, N-substituted acrylamide; and the corresponding derivatives ofmethacrylic acid. Other suitable monomers include methacrylic acid; thealkali metal and ammonium salts of methacrylic acid; methacrylamide; thevarious N-substituted methacrylamides, for example, the N-alkylsubstituted amides, the N-aminoalkyl amides, and the N-alkylaminoalkylsubstituted amides; and the aminoalkyl acrylates; the aminoalkylmethacrylamides, and the N-alkyl substituted aminoalkyl esters of eitheracrylic or methacrylic acid. Also suitable are any copolymers of theseacrylic monomers, such as the copolymers formed with polycarboxylic acidderivatives, such as maleic anhydride; maleic acid; ciumaric acid;itaconic acid; citraconic acid; aconitric acid; and the amides of theseacids; as well as the alkaline earth metal and ammonium salts of theseacids; the partial alkyl esters; salts of the partial alkyl esters andthe substituted amides of these polycarboxylic acids. The termacrylic-type monomer, therefore, denotes a monomer having an acrylicmoiety CH₂ ═CH--COOH wherein one of more hydrogen atoms may besubstituted with any radical or copolymerized or terpolymerized with anyother monomer(s) so long as the resulting polymer, having a molecularweight of 1,000 to 50,000, is water-soluble.

It has been found that these acrylic-type monomers, such as acrylicacid, neutralized in the range of 0 to 100 mole percent will polymerizerapidly to drive away excess water leaving a solid water-soluble resinhaving a desired degree of polymerization as well as new and unexpectedviscosity controlling ability in an aqueous drilling fluid. One or morepolymerization catalysts or initiators can be added to the aqueousmonomer mixture to aid in polymerization.

According to the present invention, a hot aqueous solution is preparedfirst which comprises acrylic acid neutralized 0 to 100 mole percent,and optionally acrylamide, in a mole ratio of acrylic acid to acrylamideof 70-100 mole percent acrylic acid to 30 to 0 mole percent acrylamide.The aqueous solution can be prepared easily usually by placing acrylicacid, an alkali such as potassium hydroxide and/or ammonium hydroxideand/or Na₂ CO₃ or a basic amine, for neutralizing the acid in water. Todissolve the monomers thoroughly, the mixture can be heated to anelevated temperature. Any strongly basic alkali metal compound can beused for neutralization of the acrylic acid, such as potassiumhydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide,potassium carbonate or sodium carbonate. The aqueous solution maycontain up to about 100% of free acrylic containing monomers, such asacrylic acid. Use of an excessive amount of the neutralizing agent willnot raise any particular problem, but is generally avoided since theexcess does not participate in the polymerization reaction.

We have also found that when the aqueous solution further contains anorganic solvent having a boiling point of 40° to 150° C., thetemperature of the aqueous solution is controllable with great ease.

When incorporating an organic solvent according to one embodiment of theinvention, the aqueous monomer solution has a solidifying point which isabout 10° to about 20° C. lower than otherwise. This increases theallowable range of temperature control at least about 3 times. Theorganic solvent used is vigorously evaporated along with water by theheat of polymerization of the monomer. Since the latent heat of theevaporation is considerably smaller than that of water, the organicsolvent functions as a blowing agent in the polymerization reactionsystem, consequently rendering the resulting dry resin porous.

Examples of organic solvents to be used in the invention when desiredand having a boiling point of 40° to 150° C. are methanol, ethanol,propanol and like alcohol solvents, acetone, methyl ethyl ketone andlike detone solvents, cyclohexane, n-hexane, n-heptane and likehydrocarbon solvents, benzene, toluene and like aromatic hydrocarbonsolvents, and tetrahydrofuran and like furan solvents. These solventsmay be used singly or in admixture. The solvent is used in an amount of0.5 to 15 wt. %, preferably 1 to 10 wt. %, based on the combined amountof the monomers (A) plus (B). The boiling point of the solvent is morepreferably in the range of 55° to 120° C.

In accordance with the present invention, acrylic acid neutralized 0 to100 mole percent is mixed with water at a temperature of about 20° to100° C. The solution is subjected to a polymerization reaction by theaddition of a polymerization initiator. The molecular weight must becontrolled for the resulting polymer to be useful as a viscositycontrolling agent in a drilling mud. For example, high molecular weightpolyacrylic acid is used as a thickener for water-base muds; however,low molecular weight polyacrylic acid is used as a deflocculant. Thecontrol of molecular weight can be achieved through the regulation ofreaction temperatures, starting materials, i.e., monomer and initiatorconcentrations or through the use of "scavengers", such as mercaptans,or through the introduction of functional monomers which exhibit highchain transfer capability.

The polymerization reaction proceeds sufficiently within a very shortperiod of time and the heat of the polymerization reaction willevaporate water rapidly from the reaction system to form a dry solid(less than 15 percent by weight water) low molecular weight resinwithout the need for any subsequent drying step. The solid can be easilypulverized into a powder suitable for addition to a suitable aqueousdrilling fluid to lower its viscosity.

According to the preferred process of the invention, an aqueous solutionis prepared first including an acrylic monomer neutralized 0 to 100 molepercent, optionally acrylamide, a chain transfer agent and water. Theaqueous solution can be prepared easily by placing (A) acrylic acid, andan amine, and/or a caustic alkali and/or ammonia for neutralizing theacid; (B) acrylamide (0-30 mole percent); and (C) the chain transferagent, into water to form a mixed monomer solution. To dissolve themonomer(s) thoroughly, the mixture can be heated to an elevatedtemperature up to the boiling point of water, i.e. 100° C.

The aqueous mixed monomer solution is heated and thereafter subjected topolymerization reaction with the addition of a polymerization initiator.Although the temperature of the aqueous mixed monomer solution is notparticularly limited since the mixed monomer solution is initiated intopolymerization by the addition of the initiator, the temperature isusually about 25° C. to about 85° C., preferably about 25° to about 75°C. Various polymerization initiators are usable which are known for usein preparing polyacrylates. Examples of useful initiators are redoxinitiators comprising a reducing agent, such as a sulfite or bisulfiteof an alkali metal, ammonium sulfite or ammonium bisulfite, and aninitiator, such as an alkali metal or ammonium persulfate or alkalimetal or ammonium thiosulfate, in combination with the reducing agent.The mixture need not be heated when using these redox initiators toinitiate the reaction. Other suitable initiators include azo initiatorsincluding azobis-isobutyronitrile, 4-t-butylazo-4'-cyanovaleric acid,4,4'-azobis(4-cyanovaleric acid) and2,2'-azobis(2-amidinopropane)-hydrochloric acid salt;ltrimethylolpropane triacrylate, and the like. These initiators can beused singly or in a suitable combination. Of these, especiallypreferable are a redox initiator composed of ammonium persulfate andsodium thiosulfate, and azo initiators such as azobisisobutyronitrileand 2,2'-azobis(2-amidinopropane)-hydrochloric acid. These initiatorsare advantageously used usually in the form of an aqueous solution butcan be used as diluted with a suitable solvent. The initiator is used ina usual amount, i.e. in a amount, calculated as solids, of about 0.1 toabout 10%, preferably about 0.5 to about 5%, of the combined weight ofthe monomers, namely acrylamide if present. The initiator is usabletogether with isopropyl alcohol, alkylmercaptan or other chain transferagents to control the molecular weight of the polyacrylate to a weightaverage molecular weight of about 1,000 to about 50,000.

By the addition of the polymerization initiator, the mixed monomersolution is subjected to polymerization with evaporation of waterwithout heating the system from outside. More advantageously, thereaction is carried out by admixing a predetermined amount of theinitiator and chain transfer agent, or an aqueous solution thereof, withthe mixed monomer solution and causing the resulting mixture to flowdown onto and spread over a traveling conveyor belt. The initiator canbe added to the mixed monomer solution as it is poured onto the conveyorbelt.

Briefly, the aqueous solution, including the polymerization initiators,includes an acrylic-containing monomer in an amount of 50-90% of thesolution; a neutralizing compound for the monomer in an amount of 0 to100 mole percent of the monomer; a chain transfer agent in an amount of1-10% by weight of the monomer (or other means to limit the molecularweight of the resulting polymer to a weight average molecular weight ofabout 1,000 to about 50,000); a polymerization initiator in an effectiveamount, generally about 1 to 2% by weight of the solution; and water inan amount of about 1% to about 40% by weight of the solution. The heatof polymerization is capable of completely evaporation all water from asolution containing about 20% by weight water, so that any amount ofwater in solution greater than about 20% by weight of the solution willremain absorbed in the resulting solid, water-soluble polymer. So longas the water in solution is 40% or less, a solid, water-soluble productwill result, although some of the polymer may be in solution, absorbedin the remaining, solid product.

The monovalent salt of 2-acrylamido-2-methylpropane sulfonic acid(referred to herein as AMPS a registered trademark of Lubrizonl, Inc.)also may be included in the drilling fluid additives of the presentinvention to provide the polymer with tolerance for salt contaminationfrom the surrounding formations. The structure is illustrated in thefollowing formula, where M+ represents a cation. The AMPS containingpolymers exhibit satisfactory ion stability attributable to theexceptionally large ionization constant and hydrogen bonding capabilityof AMPS units. Functionally, the AMPS units also provide fluid losscontrol capability. Monovalent salts of vinylsulfonic acid and2-sulfoethyl methacrylate also can be used in the present invention. Theconcentration of the monovalent salt of AMPS presented in the inventionmay vary from 5% to 50% by weight of the materials. ##STR1## Thepolymerization proceeds rapidly after admixing the initiator with themixed monomer solution and is completed within a short period of time,usually in about 30 seconds to about 10 minutes. The reaction isexothermic, so that the reaction system is rapidly heated to about 100°to about 130° C. by the heat of polymerization. Consequently,particularly where the acrylate monomer concentration in the mixedmonomer solution is at least 50 percent by weight and preferably atleast 70% by weight, the water evaporates from the system rapidly togive a relatively dry, solid, water-soluble polymer of low water contentwithout restoring to any external heating. The water content of thepolymer is usually up to about 15%, and generally about 8 to 12% byweight as recovered. Subsequently, the dry solid polymer can be madeinto a desired powder easily by a usual method, for example bypulverization, without a drying step.

The present invention will be described in greater detail with referenceto the following examples. The percentages of components in all examplesare by weight, unless otherwise specified.

Example 1

To deionized water are added, wherein percents are weight percents basedon the total weight of the monomer solution formed, 73.7% acrylic acidfirst, then 16.9% sodium carbonate serving as the neutralizing agent.Thereafter 7.45% of 2-mercapto ethanol chain transfer agent is added toprepare an aqueous solution of potassium sodium acrylate and acrylicacid (22% neutralization of acrylic acid).

With the aqueous solution at room temperature (25° C.) are admixed 0.4%sodium thiosulfate and 0.3% ammonium persulfate polymerizationinitiators. The final solution is as follows:

    ______________________________________                                        CHEMICALS               WT. %                                                 ______________________________________                                        ACRYLIC ACID            73.7%                                                 SODIUM CARBONATE        16.9%                                                 2-MERCAPTO ETHANOL      7.5%                                                  POLYMERIZATION INITIATORS                                                     SODIUM THIOSULFATE      0.4%                                                  AMMONIUM PERSULFATE     0.3%                                                  H.sub.2 O               1.2%                                                  TOTAL                   100.00                                                ______________________________________                                    

The admixture is poured onto a traveling endless belt and spreadthereover in the form of a layer about 10 mm in thickness. About 30seconds thereafter, the mixture starts to polymerize, and the reactionis completed in about 1 minute. The maximum temperature of the mixtureduring the reaction is about 120° C.

The polymer is allowed to complete curing for about 30 minutes atambient temperature to give a dry solid strip of sodium polyacrylate andpolyacrylic acid product having a water content of 11% and a molecularweight of 1000. The strip is made into a powder by a pulverizer.

Examples 2 to 4

Polymers are prepared in the same manner as in Example 1 with theexception of varying the concentration of monomer, the kind and amount(degree of neutralization) of neutralizing agent, and the amounts ofpolymerization initiator. The following compositions were polymerized:

EXAMPLE 2

    ______________________________________                                        ACRYLIC ACID             56.80%                                               AMMONIUM CARBONATE       11.36%                                               POLYMERIZATION INITIATOR 0.44%                                                2-MERCAPTO ETHANOL       5.0%                                                 2-ACRYLAMIDO-2-METHYLPROPANE                                                                           7.0%                                                 SULFONIC ACID                                                                 H.sub.2 O                19.4%                                                TOTAL                    100.00%                                              ______________________________________                                    

EXAMPLE 3

    ______________________________________                                        METHACRYLIC ACID       57.13%                                                 AMMONIUM CARBONATE     11.43%                                                 AZO POLYMERIZATION INITIATOR                                                                         0.5%                                                   2-MERCAPTO ETHANOL     9.0%                                                   2-ACRYLAMIDO-2-METHYLPROPANE                                                                         9.0%                                                   SULFONIC ACID                                                                 H.sub.2 O              12.87%                                                 TOTAL                  100.00%                                                ______________________________________                                    

EXAMPLE 4

    ______________________________________                                        ACRYLONITRILE          54.66%                                                 POTASSIUM HYDROXIDE    10.93%                                                 AMMONIUM HYDROXIDE     30.61%                                                 2-MERCAPTO ETHANOL     10.0%                                                  POLYMERIZATION INITIATOR                                                                             0.41%                                                  H.sub.2 O              3.39%                                                  TOTAL                  100.00%                                                ______________________________________                                    

EXAMPLE 5

To 212.2 g of deionized water are added 72.1 grams of acrylic acidfirst, then 49.5 g of potassium hydroxide having a concentration of 85%by weight and serving as a neutralizing agent, and thereafter 0.1 gramof 2-mercapto ethanol as a chain transfer agent to prepare an aqueoussolution of potassium acrylate having a neutralization degree of 75%.

With the aqueous solution at room temperature (25° C.) is admixed 2.9grams of 18% by weight aqueous solution of ammonium persulfate (about0.5 wt. % based on the combined weight of the potassium acrylate andfree acrylic acid, the same as hereinafter). The mixture is poured ontoa traveling endless belt and spread thereover in the form of a layerabout 10 mm in thickness. About 30 seconds thereafter, the mixturestarts to polymerize, and the reaction is completed in about 1 minute.The maximum temperature of the mixture during the reaction is about 120°C.

The reaction gives a dry solid strip of water-soluble potassiumpolyacrylate product having a water content of 11% and a residualmonomer concentration of 1200 ppm. The strip is made into a powder by apulverizer.

Examples 6 to 9

Methacrylic acid (72.1 grams), 18.0 grams of deionized water, 40.9 gramsof solid potassium hydroxide (water content 4%) and 5.2 grams of asolvent (Ex. 6--Acetone; Ex. 7--Ethanol, Ex. 8--Bentone; and 8% byweight 2,2'-azobis(2-amidinopropane)-hydrochloric acid salt; and Ex.9--Tetrahydrofuran) are mixed together, and the mixture is maintained at75° C. With the mixture is further admixed 4.0 grams of 2-mercaptoethanol. The resulting mixture is immediately poured onto a travelingendless belt and spread thereover to a thickness of 5 mm. About 15seconds later, the mixture starts to polymerize, and the polymerizationis completed in about 30 seconds. The maximum temperature of the mixtureduring the reaction is 130° to 135° C.

The reaction gives a dry strip of potassium polyacrylate product, whichis pulverized to a powder 20 to 100 mesh in particle size.

The same procedure as above is repeated with use of the other solvents.All the powders obtained are water-soluble and have a water content of 4to 6%.

Example 10

An aqueous monomer solution is prepared in the same manner as inexamples 6 to 9 with the exception of not using any organic solvent andusing 23.2 grams of deionized water. The solution is thereaftersubjected to polymerization in the same manner as in the previousexamples to obtain a powder of a water-soluble acrylate dry solid.

Example 11

281.0 grams of acrylic acid and 11.9 grams of acrylamide were dissolvedin 179.1 grams of distilled water and then 10.9 grams of NaOH was addedfor 70 mole percent partial neutralization of acrylic acid 0.5 gram of2-mercapto ethanol was then added as the chain transfer agent. In thisexample, 0.04 gram of 2,2'-azobis(2-amidinopropane)hydrochloride wasadded as the polymerization initiator and the initial temperature of themixed monomer solution was 50° C.

Example 12

48.1 grams of acrylic acid and 11.9 grams of acrylamide were dissolvedin 159 grams of distilled water and then 22.7 grams of NaOH was addedfor partial neutralization of acrylic acid in an amount of 85 molepercent. 1.0 grams of 2-mercapto ethanol was then added as the polyvinylmonomer. In addition, 0.048 gram of ammonium persulfate and 0.048 gramof sodium hydrogen-sulfite were added as the polymerization initiators.In this example, the initial temperature of the mixed monomer solutionwas 40° C.

Example 13

90.1 grams of methacrylic acid and 9.9 grams of acrylamide weredissolved in 118.8 grams of distilled water and 52.6 grams of KOH wasadded for 75 mole percent partial neutralization of acrylic acid. 2.0grams of 2-mercapto ethanol was added as the chain transfer agent, and0.08 grams of ammonium persulfate and 0.08 gram of sodiumhydrogen-sulfite were added as the polymerization initiators. Theinitial temperature of the mixed monomer solution was 30° C.

Example 14

48.1 grams of partially hydrolyzed acrylonitrile and 11.9 grams ofacrylamide were dissolved in 252.1 grams of distilled water. Inaddition, 5.0 grams of 2-mercapto ethanol was added as the chaintransfer agent. The polymerization was performed with the addition of0.048 gram of ammonium persulfate and 0.048 gram of sodiumhydrogen-sulfite for initiation. In this example, the initialtemperature of the mixed monomer solution was 30° C.

Example 15

52.7 grams of acrylic acid and 17.3 grams of acrylamide were dissolvedin 25 grams of distilled water and they were partially neutralized 80mole percent with the addition of 32.8 grams of KOH. 8.0 grams of2-mercapto ethanol was added as to the polyvinyl monomer. For thepolymerization catalyst 0.7 gram of 2,2'-azobisisobutyronitriledissolved in 10 cc. of acetone was added. This solution was kept at 80°C. in a TEFLON coated, glass fiber reaction chamber until completion ofpolymerization yielding a white, solid, water-soluble resin.

Example 16

17.3 grams of acrylamide was dissolved in 52.7 grams of acrylic acid andpartial (70 mole percent) neutralization of acrylic acid wasaccomplished by the addition of 30 grams of aqueous ammonia having aconcentration of 29 weight percent. In this example, for the chaintransfer agent 5 grams of 2 mercaptoethanol was added and, as theinitiator, 0.7 grams of 2,2'-azobis(2-amidinopropane)hydrochloridedissolved in 8 grams of distilled water was added. The polymerizationwas started at 80° C. yielding a white, solid, water-soluble resin.

Example 17

21 kilograms of acrylic acid and 7 kilograms of acrylamide weredissolved in 9.5 kg. of distilled water and the acrylic acid waspartially neutralized with 12 kilograms of KOH, 7.0 grams ofthioglycolic acid as a chain transfer agent was added to provide anaqueous mixed monomer solution. The mixed monomer solution was mixedwith 0.28 kilograms of 2,2'-azobisisobutyronitrile, dissolved in 2kilograms of acetone as a polymerization initiator. This mixture at atemperature of 60° C. was transferred on an endless belt (600-700 mm. inwidth, and 7 m. in length) at a thickness of about 1 cm. Thepolymerization was initiated promptly on the belt resulting in a white,solid, water-soluble resin.

Example 18

52.7 grams of acrylic acid and 17.3 grams of acrylamide were dissolvedin 20 grams of distilled water. 32.8 grams of KOH was added for 80 molepercent partial neutralization of acrylic acid. Then 4.0 grams of2-mercapto ethanol chain transfer agent was added. The aqueous monomermixture was homogenized with agitation. Next, as an initiator, 0.7 gramof 2,2'-azobisisobutyronitrile dissolved in 10 cc of acetone was added.This mixed solution was kept at 80° C. in a water bath surrounding thereaction chamber. Polymerization was initiated as the temperature of themixture increased as a result of the surrounding water bath, resultingin a white, solid, water-soluble resin.

Example 19

20.8 grams of acrylamide was dissolved in 49.2 grams of acrylic acid and28.0 grams of aqueous ammonia (29% concentration) was added for 70 molepercent neutralization of the acrylic acid. Next, 5.0 grams of2-mercapto ethanol was added and stirred to homogenize. As an initiator,0.7 gram of 2,2'azobis(2-amidinopropane)hydrochloride dissolved in 5grams of distilled water, was added. The polymerization was initiated ina TEFLON coated glass reaction chamber kept at 80° C., yielding a white,solid, water-soluble low molecular weight polymer having a water contentof about 10% by weight.

Example 20

70 grams of acrylic acid was dissolved in 20 grams of distilled water.40.8 grams of KOH was added to neutralize 75 mole percent of the acrylicacid. Next, 6.0 grams of 2-mercapto ethanol was added, and the mixturehomogenized with agitation. Then, as an initiator, 0.7 gram of2,2'-azobisisobutyronitrile dissolved in 10 cc. of acetone was added.This solution was transferred to the reaction chamber kept at 80° C. andpolymerization was initiated with a rise in temperature of the mixtureresulting in a white, solid, water-soluble low molecular weight polymerof low water content.

Example 21

52.7 grams of acrylic acid and 17.3 grams of acrylamide were dissolvedin 20 grams of distilled water. 32.8 grams of potassium hydroxide wasadded to neutralize 80 mole percent of the acrylic acid. Next, 1.5 gramsof 2-mercapto ethanol was added and homogenized under stirring. Then, asthe initiator, 0.7 gram of 2,2'-azobisisobutyronitrile dissolved in 10cc. of acetone solution was added. The mixed monomer solution was keptat 80° C. in the reaction chamber immersed in a water bath. WIth theincreasing temperature of the mixed monomer solution polymerization wasinitiated resulting in a white, solid, water-soluble, low molecularweight polymer.

Example 22

20.8 grams of acrylamide was dissolved in 49.2 grams of acrylic acid.28.0 grams of aqueous ammonia (29% concentration) was added toneutralize 70 mole percent of the acrylic acid. Then 2.0 grams of2-mercapto ethanol was added and the solution was homogenized withagitation. Next, as the initiator, 0.7 gram of2,2'-azobis(2-amidinopropane)-hydrochloride dissolved in 5 grams ofdistilled water as added. The solution was kept at 80° C. andpolymerization was initiated with increased temperature resulting in awhite, solid, water-soluble, low molecular weight polymer.

Example 23

70 grams of acrylic acid was dissolved in 20 grams of distilled waterand 40.8 grams of KOH was added to neutralize 75 mole % of the acrylicacid. Next, 3.0 grams of 2-mercapto ethanol was added and the mixturehomogenized. Next, as the initiator, 0.7 gram of2,2'-azobisisobutyronitrile dissolved in 10 cc of acetone was added. Themixed solution was kept at 80° C. in the water bath to initiate thepolymerization resulting in a white, solid, water-soluble, low molecularweight polymer.

It should be understood that the present disclosure has been made onlyby way of preferred embodiment and that numerous changes in details ofconstruction, combination and arrangement of parts may be resorted towithout departing from the spirit and scope of the invention ashereinunder claimed.

What is claimed and sought to be secured by Letters Patent of the UnitedStates is:
 1. A process for preparing a solid, essentially uncrosslinkedwater-soluble resin comprising mixing with water a monomer solution ofan acrylic monomer and 0-30 mole percent acrylamide, said acrylicmonomer neutralized 0-100 mole percent; and limiting the degree ofpolymerization of the monomer to a weight average molecular weight ofabout 1,000 to about 50,000 to form a mixed monomer solution, whereinthe monomers of the mixed monomer solution consist essentially of theacrylic monomer and optionally acrylamide, and water is present in themixed monomer solution in an amount of 1 to 40% by weight of the mixedmonomer solution, and initiating polymerization of the acrylic monomersuch that during polymerization, the exothermic heat of reaction issubstantially the only heat energy used to accomplish polymerization,and to drive off sufficient water to obtain a solid, water-soluble resinhaving a water content of 13 percent by weight or less.
 2. A process asdefined in claim 1 wherein the mixed monomer solution has a temperatureof ambient to 85° C. prior to polymerization.
 3. A process as defined inclaim 1 wherein the molecular weight is limited by including a chaintransfer agent in the mixed monomer solution.
 4. The process of claim 3wherein the chain transfer agent is a mercaptan.
 5. A process as definedin claim 1 wherein the mixed monomer solution contains 1 to 10 wt. % ofan organic solvent based on the weight of the monomer(s).
 6. A processas defined in claim 1 wherein the mixed monomer solution furthercontains an organic solvent having a boiling point of 40° to 150° C. 7.A process for preparing a solid, essentially uncrosslinked water-solublepolymer comprising:combining a monomer mixture of (A) an acrylicmonomer; and (B) 0 to 30 mole percent acrylamide, with water in anamount of at least 5.0 weight percent of (A) plus (B) based on the totalweight of (A) plus (B) plus water to form a monomer solution wherein themonomers of the monomer mixture consist essentially of (A) and (B) andthe water content of the monomer solution is 40% by weight or less;adding a polymerization initiator to said monomer mixture capable ofinitiating, and in an amount sufficient to initiate, polymerization ofsaid monomer(s) in said monomer solution; polymerizing said monomersolution while utilizing the exothermic heat of reaction assubstantially the only non-ambient energy source to drive water awayfrom said monomer solution to form said water-soluble polymer having awater content sufficiently low to be powdered without an intermediatedrying step.
 8. The process of claim 7 further including the step ofadjusting the temperature of the monomer solution to a temperature of25° to 85° C. prior to adding said polymerization initiator to saidmonomer mixture.
 9. The process of claim 7 wherein said polymerizationinitiator is added in an amount of at least 0.5% by total weight ofmonomers (A) and (B).
 10. The process of claim 7 wherein the watercontent of said water-soluble polymer is not greater than about 10% byweight as recovered from the polymerized mixture, without an additionaldrying step.
 11. The process of claim 7 further including combining anon-aqueous solvent having a boiling point of 40°-150° C. with saidmonomers (A) and (B).
 12. The process of claim 7 including the step ofpulverizing said resin to form a powder.
 13. A method of manufacturingan essentially uncrosslinked water-soluble polymer comprising mixing amonomer solution of (A) an acrylic-monomer, neutralized 0 to 100 molepercent, and (B) acrylamide in a mole ratio of (A):(B) in the range of70:30 to 100:0, and water to form a mixed monomer solution, wherein themonomers of the mixed monomer solution consist essentially of (A) and(B); and the monomer concentration in the mixture is 50-90% by weight ofthe monomer solution prior to polymerization initiation and the waterconcentration is 1% to 40% by weight of the monomer solution prior topolymerization initiation; and initiating polymerization of monomer (A)and terminating polymerization of monomer A at a weight averagemolecular weight of about 1,000 to about 50,000, such that duringpolymerization, the exothermic heat of reaction is substantially theonly heat energy used to accomplish polymerization, and to drive offsufficient water to form a solid, water-soluble acrylic-containingpolymer having a water content of 15 percent by weight or less.
 14. Themethod of claim 13 wherein the water content of said water-solublepolymer is not greater than about 10% by weight as recovered from themixed monomer solution after polymerization, without an additionaldrying step.
 15. The method of claim 14 including depositing saidmonomer mixture including said initiator onto a support surface in layerform for polymerization.